Method for manufacturing a laminate, the laminate itself, and the asphalt waterproofing layer with urethane waterproofing material.

Abstract

To suppress discoloration of an urethane coating film waterproof layer, when a laminate of a primer layer and the urethane coating film waterproof layer is provided on an asphalt waterproof layer.SOLUTION: A method for manufacturing a laminate that provides a laminate on an asphalt waterproof layer has a primer layer formation step of forming a primer layer as a curable layer of a composition for primer layer formation on the asphalt waterproof layer, and an urethane coating film formation step of forming an urethane coating film waterproof layer on the primer layer, wherein the composition for primer layer formation contains a first compound E having two or more epoxy groups in a molecule and a second compound H having two or more curable functional groups capable of reacting with the epoxy groups in the molecule, and at least one of the first compound E and the second compound H has a polysulfide structure P represented by -(R10-Sx)- (wherein, R10 is a divalent or trivalent organic group, x is an integer of 1 to 5, it satisfies at least x=2, and an average value of x is more than 1 and 2.5 or less).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a laminate provided on an asphalt waterproof layer, a laminate provided on an asphalt waterproof layer, and an asphalt waterproof layer with a urethane waterproof material.

Background Art

[0002] An asphalt waterproof layer composed of an asphalt layer is known as a waterproof layer provided on a concrete basement floor of a building or the like. As a repair method when the asphalt waterproof layer deteriorates over time, a torch method (for example, Patent Document 1) of laminating an asphalt waterproof sheet on the asphalt waterproof layer is known. In the torch method, it is necessary to use an asphalt sheet which is a heavy object and perform an operation of sticking it onto the asphalt waterproof layer to be repaired while melting the asphalt on the back surface of the sheet with a torch burner. For this reason, a worker skilled in the technique is required, and there is a problem that the working environment is severe.

[0003] Patent Document 2 describes a urethane-based coating waterproofing method suitable for waterproof applications such as the roofs, verandas, balconies, and open corridors of buildings, particularly buildings close to the living environment.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] The inventors of the present invention attempted a repair method in which a laminate of a conventional primer layer and a urethane coating waterproof layer was placed on top of an asphalt waterproof layer, and found that discoloration of the urethane coating waterproof layer was likely to occur due to the bleeding out of the asphalt components.

[0006] The present invention aims to provide a method for manufacturing a laminate that can suppress the bleed-out of asphalt components when the laminate of a primer layer and a urethane coating waterproof layer is provided on an asphalt waterproof layer. [Means for solving the problem]

[0007] The present invention has the following aspects. [1] A method for manufacturing a laminate, comprising providing a laminate on an asphalt waterproofing layer, the method comprising: a primer layer formation step of forming a primer layer which is a cured layer of a primer layer forming composition on the asphalt waterproofing layer; and a urethane coating film formation step of forming a urethane coating film waterproofing layer on the primer layer, wherein the primer layer forming composition comprises a first compound E having two or more epoxy groups in its molecule and a second compound H having two or more curable functional groups which can react with epoxy groups in its molecule, and at least one of the first compound E and the second compound H has a polysulfide structure P represented by the following formula 1, the method for manufacturing a laminate. -(R 10 -Sx)- …Formula 1 (In the formula, R 10 (where represents a divalent or trivalent organic group, x represents an integer from 1 to 5, including at least x=2, and the average value of x is greater than 1 and less than or equal to 2.5.) [2] A method for producing the laminate of [1], wherein the first compound E comprises compound E1 having the polysulfide structure P. [3] A method for producing the laminate of [2], wherein the compound E1 comprises compound E11 represented by the following formula 2.

[0008] [ka]

[0009] (In the formula, R1 and R 3 each independently represents an organic group, and R 2 represents an organic group containing -(R 4 -Sx)-, and R 4 represents a divalent or trivalent organic group, x represents an integer from 1 to 5, including at least x = 2, and the average value of x is greater than 1 and less than or equal to 2.5.) [4] The method for producing a laminate according to any one of [1] to [3], wherein the second compound H contains a compound H1 having the polysulfide structure P. [5] The method for producing a laminate according to [4], wherein the compound H1 contains a compound H11 represented by the following formula 6. HS-(R 11 -Sx) n -R 11 -SH... Formula 6 (In the formula, R 11 represents a divalent organic group containing an -O-CH2-O- bond or a trivalent organic group containing -CH2C(H)CH2-, n represents the repeating number of (R 11 -Sx) and is an integer from 1 to 200, x is an integer from 1 to 5, including at least x = 2, and the average value of x is greater than 1 and less than or equal to 2.5.) [6] The method for producing a laminate according to any one of [1] to [5], wherein the composition for forming the primer layer further contains a curing catalyst. [7] The method for producing a laminate according to any one of [1] to [6], wherein the content ratio of the epoxy groups to the total number of moles of the epoxy groups and the polysulfide structure P contained in the composition for forming the primer layer is 40 to 90 mol%. [8] In the primer layer forming step, the composition for forming the primer layer is applied onto the asphalt waterproof layer at an application amount of 0.1 to 1.0 kg / m 2 and cured to form the primer layer. The method for producing a laminate according to any one of [1] to [7]. [9] A method for producing a laminate according to any one of [1] to [8], wherein in the urethane coating film forming step, a mixture of a main component composition containing an isocyanate group-terminated prepolymer obtained by reacting a polyol with a polyisocyanate compound and a curing agent composition containing a compound having an active hydrogen-containing group is applied onto the primer layer.

[0010]

[10] A laminate provided on an asphalt waterproofing layer, the laminate comprising a primer layer on the asphalt waterproofing layer and a urethane coating waterproofing layer on the primer layer, wherein the primer layer comprises a reaction product of a first compound E having two or more epoxy groups in its molecule and a second compound H having two or more curable functional groups in its molecule that can react with epoxy groups, the reaction product having a polysulfide structure P represented by the following formula 1, and the urethane coating waterproofing layer comprising a reaction product of an isocyanate group-terminated prepolymer obtained by reacting a polyol with a polyisocyanate compound and a compound having an active hydrogen-containing group. -(R 10 -Sx)- …Formula 1 (In the formula, R 10 (where represents a divalent or trivalent organic group, x represents an integer from 1 to 5, including at least x=2, and the average value of x is greater than 1 and less than or equal to 2.5.)

[11] An asphalt waterproof layer with a urethane waterproofing material, comprising an asphalt waterproof layer and a urethane waterproofing material covering the asphalt waterproof layer, wherein the urethane waterproofing material includes a laminate of

[10] . [Effects of the Invention]

[0011] According to the present invention, when a laminate of a primer layer and a urethane coating waterproof layer is provided on an asphalt waterproof layer, the bleed-out of asphalt components can be suppressed. [Modes for carrying out the invention]

[0012] The following definitions of terms apply throughout this specification and the claims. A numerical range represented by "~" means a range of numbers whose lower and upper limits are the numbers before and after the "~". An "active hydrogen-containing group" is at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a monovalent functional group obtained by removing one hydrogen atom from a primary amine, and a thiol group, all of which are bonded to a carbon atom. "Active hydrogen" refers to hydrogen atoms based on the active hydrogen-containing group and hydrogen atoms based on the hydroxyl group of water. In this specification, the number-average molecular weight is the polystyrene-equivalent molecular weight obtained by measuring it by gel permeation chromatography (GPC) using a calibration curve prepared with standard polystyrene samples of known molecular weight.

[0013] ≪Method for manufacturing laminates≫ The manufacturing method of the laminate according to this embodiment includes the steps of forming a primer layer, which is a hardened layer of a primer layer forming composition, on an asphalt waterproofing layer (primer layer formation step), and forming a urethane coating waterproofing layer on the primer layer (urethane coating formation step).

[0014] <Composition for forming primer layer> The primer layer-forming composition comprises a first compound E having two or more epoxy groups in its molecule, and a second compound H having two or more curable functional groups in its molecule that can react with epoxy groups. At least one of the first compound E and the second compound H has a polysulfide structure P represented by the following formula 1.

[0015] -(R 10 -Sx)- …Formula 1 In Equation 1, R 10 R represents a divalent or trivalent organic group. 10 Examples include either a divalent organic group containing an -O-CH2-O- bond or a trivalent organic group containing -CH2C(H)CH2-, with -CH2CH2OCH2OCH2CH2- or -CH2C(H)CH2- being examples. In equation 1, x represents an integer from 1 to 5. The polysulfide structure P represented by formula 1 may be present in one or more molecules, and may be present in quantities of 1 to 50. The polysulfide structure P represented by formula 1 includes at least x=2, and the average value of x is greater than 1 and less than or equal to 2.5.

[0016] In a primer layer-forming composition, the first compound E includes either or both of compound E1 having a polysulfide structure P and compound E0 not having a polysulfide structure P. In a primer layer-forming composition, the second compound H comprises either or both of compound H1 having a polysulfide structure P and compound H0 not having a polysulfide structure P. The first compound E and the second compound H are combined such that the primer layer-forming composition contains at least one of compound E1 and compound H1.

[0017] <Compound E1> Compound E1 is a compound having two or more epoxy groups in its molecule and a polysulfide structure P represented by formula 1. Compound E1 may be used alone or in combination of two or more types. Compound E1 is preferably compound E11, represented by the following formula 2.

[0018] [ka]

[0019] In Equation 2, R 1 and R 3 Each of these independently represents an organic group, R 2 ha-(R 4 R represents an organic group containing -Sx)-. 4 x represents a divalent or trivalent organic group, x represents an integer from 1 to 5, including at least x=2, and the average value of x is greater than 1 and less than or equal to 2.5. R 2 For example, -Z-(R 4 -Sx)mR 5 It is -Y-. R 5R represents a divalent or trivalent organic group. 4 , R 5 They may be the same or different. 4 , R 5 A preferred embodiment is R 10 It is similar to that. Y and Z are divalent groups selected from -S-, -O-, and -NH-. Y and Z may be the same or different. m is an integer between 1 and 50. x is an integer between 1 and 5, and when there are multiple Sx, x may be the same or different from each other. Of the m Sx, at least one is x=2, and the average value of x is greater than 1 and less than or equal to 2.5.

[0020] In Equation 2, R 1 or R 3 The organic group is preferably the group represented by the following formulas 3 to 5. In formulas 3 to 5, b represents an integer of 1 or more, preferably 1 to 20, and R 6 This is either a hydrogen atom or a methyl group. -(OCH2CH2) b -OCH2CH(OH)CH2- …Formula 3 -(-OCH2CH(OH)CH2- …Formula 4

[0021] [ka]

[0022] Compound E11 is, in formula 2 above, R 1 and R 3 R is a divalent group represented by formula 5, 2 ga-S-(R 4 -SS) m -R 5 -S- and R 4 and R 5 Compounds in which all of the groups are -(CH2CH2OCH2OCH2CH2)- are preferred. The molecular weight of compound E11 is preferably 200 to 2,000, and more preferably 300 to 1,600. The epoxy equivalent of compound E11 is preferably 100 to 1,000 g / eq, and more preferably 150 to 800 g / eq. Such compounds are available commercially. For example, Toray Fine Chemicals' products "Frep-50" and "Frep-60" are examples.

[0023] <Compound E0> Compound E0 is a compound that has two or more epoxy groups in its molecule and does not contain the polysulfide structure P represented by formula 1. Compound E0 may be used alone or in combination of two or more types. Compound E0 can be any compound known in the field of epoxy resin primers. Examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. Bisphenol A type epoxy resin is preferred because it easily increases the hardness of the formed primer layer. Compound E0 preferably has two epoxy groups per molecule (bifunctional). The molecular weight of compound E0 is preferably 200 to 2,000, and more preferably 300 to 1,600. The epoxy equivalent of compound E0 is preferably 100 to 1,000 g / eq, and more preferably 150 to 800 g / eq.

[0024] <Compound H1> Compound H1 is a compound having two or more curable functional groups that can react with epoxy groups within its molecule, and having a polysulfide structure P represented by formula 1. Compound H1 may be used alone or in combination of two or more types. The curable functional group of compound H1 is preferably a thiol group. The compound H1 preferably has two curable functional groups (bifunctional) per molecule. Compound H1 is preferably compound H11, represented by the following formula 6.

[0025] HS-(R 11 -Sx) n-R 11 -SH…Formula 6 In Equation 6, R 11 The expression represents a divalent organic group containing an -O-CH2-O- bond or a trivalent organic group containing -CH2C(H)CH2-, where n is an integer from 1 to 200, and x is an integer from 1 to 5, including at least x=2, with the average value of x being greater than 1 and less than or equal to 2.5.

[0026] Multiple R molecules exist within a single molecule. 11 They may be the same or different from each other. R 11 This may be a trivalent organic group containing an -O-CH2-O- bond and a branched trivalent group obtained by removing the halogen atom from a trihaloalkane. A trihaloalkane is, for example, trihalopropane. R 11 It is more preferable that the group is a divalent group represented by -C2H4-O-CH2-O-C2H4-. R present in one molecule 11 The content of -C2H4-O-CH2-O-C2H4- relative to the total number of moles is preferably 50 mol% or more, and more preferably 70 mol% or more. It may also be 100 mol%. n is (R 11 This represents the number of repetitions of -Sx) and is an integer between 1 and 200. x is an integer between 1 and 5, and when there are multiple Sx, x may be the same or different from each other. Of the n Sx, at least one is x=2, and the average value of x is greater than 1 and less than or equal to 2.5.

[0027] Compound H11 is R in formula 6 above. 11 Compounds in which the divalent group is represented by -C2H4-O-CH2-O-C2H4- and x is 2 are preferred. The number-average molecular weight of compound H11 is preferably 500 to 10,000, and more preferably 800 to 8,000. The thiol group content in compound H11 is preferably 0.5 to 10% by mass, and more preferably 1 to 8% by mass. Such compounds are available commercially. For example, the "Thiokol LP" series from Toray Fine Chemicals is one such example. As compound H11, Toray Fine Chemicals' product name "Thiokol LP-3" is preferred.

[0028] <Compound H0> Compound H0 is a compound that has two or more curable functional groups that can react with epoxy groups within its molecule, and does not contain the polysulfide structure P represented by formula 1. Compound H0 may be used alone or in combination of two or more types. Compound H0 can be a known compound used as a curing agent in the field of epoxy resin primers. Examples of curable functional groups for compound H0 include amino groups, thiol groups, sulfonic acid groups, and hydroxyl groups. Amino groups or thiol groups are preferred, with amino groups being more preferred, due to their better reactivity with epoxy groups. The number of curable functional groups in one molecule of compound H0 is preferably two (bifunctional) or three (trifunctional), and more preferably three.

[0029] Compound H0 is preferably, for example, an aliphatic polyamine or a polyether polyamine. Of the aliphatic polyamines, linear aliphatic polyamines are more preferred. Polyether polyamines are compounds having polyoxyalkylene chains with an amino group (-NH2) at the terminal. The polyoxyalkylene chains preferably contain an oxypropylene group. Examples of polyether polyamines include triethylene glycol diamine, polyoxypropylene diamine, polyoxypropylene triamine, trimethylolpropane poly(oxypropylene)triamine, and glyceryl poly(oxypropylene)triamine. The molecular weight of the polyether polyamine is preferably 200 to 5,000, and more preferably 300 to 4,000. When the primer layer-forming composition contains water as a solvent, it is preferable to use a water-soluble amine compound as compound H0. Examples of water-soluble amine compounds include aliphatic polyamines and modified polyamidoamines. The active hydrogen equivalent of the water-soluble amine compound is preferably 80 to 1,000 g / eq, and more preferably 100 to 400 g / eq.

[0030] <Curing catalyst> The primer layer formation composition preferably contains a curing catalyst. For the curing catalyst, compounds known as curing catalysts in the field of epoxy resin primers can be used. For example, known amine-based curing agents can be used. Amine-based curing agents include aliphatic tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, and dimethyldodecylamine; aromatic tertiary amines such as dimethylbenzylamine and triphenylamine; alicyclic tertiary amines such as dimethylcyclohexylamine; hydroxyl group-containing tertiary amines such as 3-dimethylamino-1-propanol, 2-dimethylaminoethanol, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol; and triethylenediamine. Examples include cyclic tertiary amines such as n; polyamine tertiary amines such as N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, and N,N,N',N'',N''-pentamethyldiethylenetriamine; hydroxyl group-containing secondary amines such as diisopropanolamine; and amino-functional silanes containing primary amino groups and alkoxysilyl groups such as N-β-aminoethyl-γ-aminopropyltrimethoxysilane. Of these, tertiary amines such as aliphatic tertiary amines, aromatic tertiary amines, alicyclic tertiary amines, hydroxyl group-containing tertiary amines, cyclic tertiary amines, and polyamine-based tertiary amines are preferred.

[0031] <Optional ingredients> The primer layer-forming composition may contain any components other than the first compound E, the second compound H, and the curing catalyst. Any optional components can be those known in the field of epoxy resin primers. Examples include organic solvents, water, emulsifiers / dispersants, anti-repellent agents, plasticizers, fillers, antioxidants, flame retardants, stabilizers, UV absorbers, and coloring pigments. Examples of organic solvents include methylcyclohexane, n-heptane, n-decane, cyclohexanone, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, xylene, toluene, petroleum hydrocarbons, methanol, ethanol, isobutyl alcohol, isopropyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monotyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and dimethyl carbonate. When using an organic solvent, the amount of the organic solvent is preferably 1 to 70% by mass, and more preferably 3 to 50% by mass, relative to the total mass of the primer layer forming composition. When water is used, the amount of water is preferably 1 to 70% by mass, and more preferably 3 to 50% by mass, relative to the total mass of the primer layer forming composition.

[0032] <Content> The ratio of epoxy groups to the total number of moles of polysulfide structure P in the primer layer-forming composition is preferably 40 to 90 mol%, more preferably 45 to 90 mol%, and even more preferably 50 to 85 mol%. If the ratio is above the lower limit of the above range, the primer layer will have excellent flexibility and a superior effect in suppressing bleed-out. If the ratio is below the upper limit, the primer layer will be less prone to cracking. It is preferable that the first compound E and the second compound H be combined such that the content ratio of the epoxy groups falls within the above range. For example, the amount of the second compound H is preferably 15 to 200 parts by mass, and more preferably 20 to 120 parts by mass, relative to 100 parts by mass of the first compound E. When a curing catalyst is used, the amount of curing catalyst is preferably 1 to 30 parts by mass, and more preferably 2 to 20 parts by mass, per 100 parts by mass of the first compound E.

[0033] <Preferred embodiment of the primer layer forming composition> The primer layer-forming composition is preferably in the following embodiment 1 or embodiment 2. Embodiment 1: An embodiment in which the content of compound E1 is greater than 50% by mass and 100% by mass or less, preferably 55 to 100% by mass, relative to the total mass of the first compound E, and the content of compound H0 is greater than 50% by mass and 100% by mass or less, preferably 60 to 100% by mass, relative to the total mass of the second compound H. Embodiment 2: An embodiment in which the content of compound E0 is greater than 50% by mass and 100% by mass or less, preferably 55 to 100% by mass, relative to the total mass of the first compound E, and the content of compound H1 is greater than 50% by mass and 100% by mass or less, preferably 60 to 100% by mass, relative to the total mass of the second compound H.

[0034] [Aspect 1] In Embodiment 1, the amount of the second compound H is preferably 10 to 60 parts by mass, and more preferably 20 to 55 parts by mass, per 100 parts by mass of the first compound E. If the amount is above the lower limit of the above range, the curability when forming the primer layer tends to be better, and if it is below the upper limit, the formed primer layer tends to be more flexible and bleed-out from the asphalt layer tends to be suppressed. When a curing catalyst is used, the amount of curing catalyst is preferably 1 to 30 parts by mass, and preferably 2 to 20 parts by mass, per 100 parts by mass of the first compound E. If the amount is above the lower limit of the above range, the curability when forming the primer layer will be better, and if it is below the upper limit, the strength of the primer layer will be better. In embodiment 1, it is preferable that compound H0 contains a polyether polyamine in that it provides better curability when forming the primer layer. In Embodiment 1, when the primer layer forming composition contains water, it is preferable to use a water-soluble amine compound as compound H0.

[0035] [Aspect 2] In embodiment 2, the amount of the second compound H is preferably more than 50 parts by mass and 100 parts by mass or less, and more preferably 60 to 100 parts by mass, per 100 parts by mass of the first compound E. If the amount is above the lower limit of the above range, the curability when forming the primer layer tends to be better, and if it is below the upper limit, the formed primer layer tends to be more flexible and bleed-out from the asphalt layer tends to be better suppressed. When a curing catalyst is used, the amount of curing catalyst is preferably 1 to 30 parts by mass, and preferably 2 to 20 parts by mass, per 100 parts by mass of the first compound E. If the amount is above the lower limit of the above range, the curability when forming the primer layer will be better, and if it is below the upper limit, the strength of the primer layer will be better. In embodiment 2, it is preferable that compound E0 contains a bisphenol A type epoxy resin, as this results in better hardness of the primer layer.

[0036] <Method for producing a primer layer-forming composition> The primer layer-forming composition is prepared by preparing and storing a first composition containing the first compound E and a second composition containing the second compound H, and mixing the two at the time of use. It is preferable that optional components other than the solvent and water be included in the first composition.

[0037] <Primer layer formation process> In the primer layer formation process, a primer layer formation composition is applied to the asphalt waterproofing layer and cured to form the primer layer. The underlying asphalt waterproofing layer may be a waterproofing layer applied by heating and melting an asphalt composition containing waterproofing asphalt, or it may be a sheet waterproofing layer made of asphalt sheets. The primer layer-forming composition can be applied using known application methods such as roller application, brush application, or spray application.

[0038] The application rate of the primer layer-forming composition is 0.1 to 1.0 kg / m². 2 Preferably, 0.15~0.8 kg / m 2This is more preferable. If the value is above the lower limit of the above range, it is easier to suppress the bleeding out of asphalt components when the laminate of the primer layer and the urethane coating waterproof layer is placed on the asphalt waterproof layer. If the value is below the upper limit, the primer layer hardens more easily and workability is improved. The thickness of the primer layer after curing can be adjusted by the amount of solvent or water contained in the primer layer forming composition and the amount applied. For example, 100 μm to 1.0 mm is preferred, and 200 μm to 0.5 mm is more preferred.

[0039] In the subsequent urethane coating process, it is preferable that the curing time of the primer layer-forming composition not be too long so that an operator can work on the cured primer layer. The curing properties of the primer layer-forming composition are preferably such that the touch-dry time at 23°C is 1 to 5 hours. This range is preferable in terms of shortening the construction period. The touch-dry time in this specification is the value obtained by the measurement method specified in JIS K5600-1-1 (1999).

[0040] <Urethane coating formation process> Next, a urethane coating composition is applied onto the cured primer layer and cured to form a urethane waterproof coating layer. The urethane coating film-forming composition is a mixture of a main component composition containing an isocyanate-terminated prepolymer obtained by reacting a polyol with a polyisocyanate compound, and a curing agent composition containing a compound having an active hydrogen-containing group (hereinafter also referred to as an active hydrogen compound). The main component composition and curing agent composition can be those known for use in urethane coating waterproofing layers.

[0041] The polyol, polyisocyanate compound, and isocyanate-terminated prepolymer constituting the main composition can be, for example, those described in Japanese Patent Application Publication No. 2007-119665.

[0042] The polyol is preferably a polyether polyol obtained by addition polymerization of propylene oxide or propylene oxide and ethylene oxide to an initiator having two or three active hydrogens in one molecule. The number-average molecular weight of the polyether polyol is preferably 800 to 8,000, and more preferably 1,000 to 5,000. One type of polyol may be used, or two or more types may be used in combination.

[0043] Polyisocyanate compounds include aromatic diisocyanate compounds such as tolylene diisocyanate (TDI), 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), α,α,α',α'-tetramethylxylylene diisocyanate, 4,4'-dibenzyle diisocyanate, tolidine diisocyanate, 1,5-naphthalene diisocyanate, etc.; tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate ( Linear or branched aliphatic diisocyanate compounds such as HDI, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dodecamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate; norbornane diisocyanate (NBDI), isophorone diisocyanate (IPDI), hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, and dicyclohexylmethane diisocyanate (H 12 Examples include alicyclic diisocyanate compounds such as MDI; and aromatic aliphatic diisocyanate compounds such as dialkyldiphenylmethane diisocyanate and tetraalkyldiphenylmethane diisocyanate. Aromatic diisocyanate compounds are preferred as the polyisocyanate compound. TDI and MDI are more preferred because they allow for a shorter curing time and thus a shorter construction period, and TDI is even more preferred because it is easier to handle. One polyisocyanate compound may be used, or two or more may be used in combination. When synthesizing isocyanate-terminated prepolymers by reacting a polyol with a polyisocyanate compound, the molar ratio of NCO / OH is preferably 1.5 to 12.0. For TDI, 1.5 to 3.0 is more preferable. For MDI, 8.0 to 12.0 is more preferable. The NCO group content is preferably 2.0 to 12.0% by mass relative to the total mass of the isocyanate-terminated prepolymer. For TDI, 2.0 to 7.0% by mass is more preferable. For MDI, 8.0 to 12.0% by mass is more preferable. The number-average molecular weight of the isocyanate-terminated prepolymer is preferably 500 to 150,000, and more preferably 1,000 to 100,000.

[0044] The main component composition may contain one or more optional components other than the isocyanate group-terminated prepolymer. These optional components may be those known in the main component compositions of urethane coating waterproofing layers. For example, optional components described in paragraphs 0038 to 0040 of Japanese Patent Application Publication No. 2007-119665 may be used. Specific examples include organic solvents, catalysts, and plasticizers.

[0045] The active hydrogen compound constituting the curing agent composition can be, for example, an active hydrogen compound (amine curing agent) described in Japanese Patent Publication No. 2015-91965. For active hydrogen compounds, amino groups and hydroxyl groups are preferred as active hydrogen-containing groups. Specific examples of active hydrogen compounds having an amino group include bis-aromatic primary diamines such as 4,4'-methylenebis(2-chloroaniline), 4,4'-methylenebis(3-chloro-2,6-diethylaniline), and bis(methylthio)toluenediamine, as well as diethyltoluenediamine. Specific examples of active hydrogen compounds having hydroxyl groups include polyether polyols obtained by addition polymerization of propylene oxide or propylene oxide and ethylene oxide to an initiator having two or three active hydrogens in one molecule. One active hydrogen compound may be used, or two or more may be used in combination.

[0046] The curing agent composition may contain one or more optional components other than active hydrogen compounds. These optional components are those known in curing agent compositions for urethane coating waterproofing layers. For example, optional components described in paragraphs 0047 to 0053 of Japanese Patent Application Publication No. 2007-119665 can be used. Specific examples include plasticizers such as diisononyl phthalate, inorganic fillers such as calcium carbonate, pigments, catalysts such as lead 2-ethylhexanoate, wetting and dispersing agents, defoaming agents, antioxidants, UV absorbers, and dehydrating agents.

[0047] In the process of preparing a urethane coating film-forming composition by mixing the main component composition and the curing agent composition, the ratio of moles of NCO groups in the main component composition to moles of active hydrogen in the curing agent composition, expressed as NCO / active hydrogen, is preferably 0.8 / 1 to 2.0 / 1, and more preferably 1.0 / 1 to 1.6 / 1.

[0048] The urethane coating film-forming composition can be applied using known application methods such as roller application, brush application, or spray application. The amount of urethane coating composition applied can be set to achieve the desired thickness. It may be applied in two or more coats. For example, the total amount of urethane coating composition applied is 0.1 to 5.0 kg / m². 2 Preferably, 2.0 to 4.0 kg / m 2 This is more preferable. If the value is above the lower limit of the above range, the waterproofing layer is less likely to break, and if it is below the upper limit, the number of application coats can be kept to a minimum, which is preferable in terms of workability. The thickness of the urethane coating waterproof layer after curing is preferably 1.0 to 5.0 mm, and more preferably 2.0 to 3.0 mm.

[0049] ≪Laminated structure≫ The laminate obtained by the manufacturing method of this embodiment has a primer layer and a urethane coating waterproof layer on the primer layer. The primer layer is located on the asphalt waterproof layer. The primer layer contains a reactant obtained by the reaction of the epoxy group of the first compound E with the curable functional group of the second compound H. This reactant is a specific epoxy resin having a polysulfide structure P derived from one or both of the first compound E and the second compound H. The urethane coating waterproof layer contains a reaction product (urethane resin, urea resin) formed by the reaction of isocyanate groups of isocyanate-terminated prepolymers with active hydrogen-containing groups of active hydrogen compounds.

[0050] The laminate of this embodiment may further have layers other than the primer layer and the urethane waterproof coating layer. For example, it may have a protective finish coating (topcoat layer) on the urethane waterproof coating layer. For the protective finish coating, known curing agent compositions for urethane coating waterproof layers can be used. For example, the topcoat layer forming composition described in Japanese Patent Application Publication No. 2002-250099 can be used.

[0051] ≪Asphalt waterproofing layer with urethane waterproofing material≫ The laminate of this embodiment is suitable as a waterproofing material for covering an asphalt waterproofing layer because it can suppress discoloration due to the bleeding out of asphalt components even when in contact with an asphalt layer. The asphalt waterproofing layer with urethane waterproofing material of this embodiment comprises an asphalt waterproofing layer and a urethane waterproofing material covering the asphalt waterproofing layer, wherein the urethane waterproofing material includes the laminate of this embodiment.

[0052] According to this embodiment, for example, when an asphalt waterproofing layer deteriorates over time, it can be repaired by providing the laminate of this embodiment (urethane waterproofing material) on top of the asphalt waterproofing layer. As shown in the examples described later, if the primer layer is a conventional urethane resin-based primer, the asphalt components bleed out, causing yellowing of the urethane coating waterproof layer. In contrast, the primer layer of this embodiment contains a specific epoxy resin having a polysulfide structure P, and is excellent in suppressing the bleeding out of asphalt components. Furthermore, if the primer layer is too rigid, cracking may occur, potentially leading to bleed-out from the cracks. As shown in the examples described later, the primer layer of this embodiment is also highly flexible, making it less prone to cracking and providing excellent protection against bleed-out from cracks. [Examples]

[0053] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

[0054] <Evaluation Method> [Cureability test] The sand on the surface of a sand-coated asphalt sheet (Nisshin Kogyo Co., Ltd. product name "Meltan Cap 21F") was burned off with a torch to create a test substrate with an asphalt surface. Apply 0.2 kg / m² of the primer layer-forming composition for each example to the asphalt surface of the test substrate. 2 The primer was applied using the specified amount. After application, it was left to stand in an atmosphere of 23±2℃ and 50±10% relative humidity. The thickness of the primer layer was 0.1 to 0.3 mm. The touch-dry time was measured by checking the curing state by touch every hour. If the touch-dry time was within 5 hours, the curing performance was evaluated as good (○); if it exceeded 5 hours, the curing performance was evaluated as poor (×).

[0055] [Bleed test: Bleed resistance] In the same manner as in the curing test described above, each example of primer layer-forming composition was applied to the asphalt surface of the test substrate, and the mixture was cured until hardening was confirmed by touch to form a primer layer. On the resulting primer layer, the urethane coating composition obtained in Preparation Example 1 below was added at a rate of 1.3 kg / m².2 The primer was applied using the specified amount. After application, the surface was left to stand for 24 hours in an atmosphere of 23±2℃ and 50±10% relative humidity to form a urethane waterproof coating layer on top of the primer layer. Subsequently, it was left to stand for one week in a constant temperature chamber at 80℃. The thickness of the urethane waterproof coating layer was approximately 1 mm. The surface of the urethane coating waterproofing layer was visually inspected to check for yellowing. The total area of ​​the urethane coating waterproofing layer and the area of ​​the yellowed portion were measured and evaluated according to the following criteria. (Judgment criteria) ○: The area of ​​the yellowed portion was 10% or less of the total area. △: The area of ​​the yellowed portion was between 10% and 90% of the total area. ×: Yellowing was observed in over 90% of the total area.

[0056] [Preparation Example 1: Preparation of a composition for forming a urethane coating] The urethane waterproofing coating material used met the standards for high-elongation urethane rubber-based materials as specified in JIS A 6021:2011. 61.2 parts by mass of polyoxypropylenediol (number average molecular weight: 2000), 23.6 parts by mass of polyoxypropylenetriol (number average molecular weight: 3000), and 15.2 parts by mass of tolylene diisocyanate (2,4-isomer 80% by mass) were reacted (NCO / OH molar ratio = 2.06) to synthesize an isocyanate-terminated polyurethane prepolymer with an NCO group content of 3.78% by mass. The resulting reaction product was used as the main composition. Separately, 3.90 parts by mass of MBOCA (4,4'-methylenebis(2-chloroaniline)) was dissolved in 18.0 parts by mass of polyoxypropylenetriol (average molecular weight; 5000) at 80°C, and then cooled to room temperature. Next, 15.6 parts by mass of diisononyl phthalate, 58.0 parts by mass of calcium carbonate, 3.0 parts by mass of pigment paste, 1.0 part by mass of lead 2-ethylhexanoate, 0.2 parts by mass of a wetting dispersant, and 0.3 parts by mass of an antifoaming agent were added and mixed to obtain a curing agent composition. A urethane coating film-forming composition was obtained by mixing the main component composition and the curing agent composition so that the molar ratio of NCO to active hydrogen was 1.10.

[0057] [Flexibility Test] A frame measuring 25 mm in length, 120 mm in width, and 2 mm in height was placed on a Teflon®-coated iron plate, and the primer layer-forming composition for each example was poured into the frame. After standing for 4 days in an atmosphere of room temperature (23°C ± 2°C) and relative humidity of 50% ± 10%, the material was removed from the frame, turned over, and left to harden for another 3 days. The resulting hardened material was used as a test specimen. The thickness of the test specimen in the short-side direction (height direction of the frame) was measured at three arbitrary points using a thickness measuring instrument, and the median value was taken as the representative value. The obtained test specimens were bent along the outer surface of a cylindrical bending machine and held for 3 seconds. If no cracks were observed visually, the specimen was judged as good (○), and if cracks occurred, it was judged as poor (×). Three types of bending machines were used, each with a diameter of 95mm, 77mm, and 50mm. The largest diameter was used first in the test, and the test was terminated when cracking occurred. A smaller diameter at which cracking did not occur indicates higher flexibility.

[0058] [comprehensive evaluation] From the perspective of suppressing bleed-out in laminates on asphalt waterproofing layers, those that passed both the bleed test and the flexibility test were given an overall rating of ○, while all others were given a ×.

[0059] <Raw materials used> [First compound] ·E1-1: Toray Fine Chemicals Co., Ltd. product name "Frep-50", in formula 2, R 1 and R 3 This is a divalent group represented by formula 5, and R 2 ga-S-(R 4 -SS) m -R 5 -S- and R 4 and R 5 is -(CH2CH2OCH2OCH2CH2)-, and R 6 A compound in which the atom is a hydrogen atom, with a molecular weight of 640 and an epoxy equivalent of 320 g / eq. ·E0-1: Mitsubishi Chemical Corporation product name "jER828", bisphenol A type epoxy resin, 2 epoxy atoms per molecule (bifunctional), molecular weight 370, epoxy equivalent 185 g / eq.

[0060] [Second compound] ·H1-1: Toray Fine Chemicals Co., Ltd. product name "Thiokol LP-3", in formula 6, R 11 A compound with the structure -C2H4-O-CH2-O-C2H4-, an average value of x of 2, a number-average molecular weight of 1000, and a sulfanyl group content of 6.6% by mass. • H0-1: Huntsman product name "JEFFAMINE T-403", polyoxypropylene triamine, molecular weight 440. • H0-2: Adeka Corporation product name "Adeka Hardener WEH-102", water-soluble amine compound, active hydrogen equivalent (g / eq) = 120.

[0061] [Curing catalyst] • Curing catalyst (1): 2,4,6-tris(dimethylaminomethyl)phenol. [Optional ingredients] • Anti-repellent agent (1): Kusumoto Chemical Co., Ltd. product name "SEI-1502", acrylic polymer, viscosity (20℃) 3.6 Pa·s. • Emulsifier / dispersant (1): Kao Chemical Co., Ltd. product name "Emulgen A-60", polyoxyethylene distylenide phenyl ether. [solvent] • Solvent (1): Methylcyclohexane (MCH). [Comparative primer] • Comparative primer (1): AGC Polymer Building Materials Co., Ltd. product name "PJ Primer", urethane resin-based primer composition, solvent is methylcyclohexane. • Comparative primer (2): AGC Polymer Building Materials Co., Ltd. product name "Saracene P", urethane resin-based primer composition, solvents are xylene, ethylbenzene, and ethyl acetate.

[0062] <Examples 1-7> Examples 1-4 are examples of actual cases, and Examples 5-7 are comparative examples. A primer layer-forming composition was prepared by mixing the components shown in Table 1. The curability, bleed-out suppression, and flexibility of the cured product of the obtained primer layer-forming composition were evaluated using the method described above. The results are shown in Table 1.

[0063] [Table 1]

[0064] As shown in the table, the primer-forming compositions of Examples 1-4 exhibited good curability, and the cured product (primer layer) had excellent flexibility and bleed resistance. The urethane resin-based primers in Examples 5 and 6 exhibited poor bleeding resistance. The epoxy resin primer in Example 7, which did not contain the polysulfide structure P, showed good bleed resistance in the bleed test, but cracked in the flexibility test, indicating that it was insufficient in suppressing bleed-out as a primer layer applied on an asphalt waterproofing layer.

Claims

1. A method for manufacturing a laminate, comprising providing a laminate on an asphalt waterproofing layer, a urethane coating waterproofing layer, and a topcoat layer on the urethane coating waterproofing layer, The process includes a primer layer formation step of forming a primer layer, which is a hardened layer of a primer layer formation composition, on the asphalt waterproof layer, and a urethane coating formation step of forming the urethane coating waterproof layer on the primer layer. The primer layer forming composition comprises a first compound E having two or more epoxy groups in its molecule, and a second compound H having two or more curable functional groups in its molecule that can react with epoxy groups. At least one of the first compound E and the second compound H has a polysulfide structure P represented by the following formula 1, A method for producing a laminate, comprising applying a mixture of a main component composition containing an isocyanate group-terminated prepolymer obtained by reacting a polyol with a polyisocyanate compound, and a curing agent composition containing a compound having an active hydrogen-containing group, onto the primer layer in the urethane coating film formation step. - (R) １０ -Sx)- ...Formula 1 (In the formula, R １０ (where represents a divalent or trivalent organic group, x represents an integer from 1 to 5, including at least x=2, and the average value of x is greater than 1 and less than or equal to 2.5.)

2. The method for producing a laminate according to claim 1, wherein the first compound E comprises compound E1 having the polysulfide structure P.

3. The method for producing a laminate according to claim 2, wherein the compound E1 includes a compound E11 represented by the following formula 2. 【Chemistry 1】 (In the formula, R １ and R ３ Each of these independently represents an organic group, R ２ ha- (R ４ Represents an organic group containing -Sx)-, R ４ (where represents a divalent or trivalent organic group, x represents an integer from 1 to 5, including at least x=2, and the average value of x is greater than 1 and less than or equal to 2.5.)

4. The method for producing a laminate according to claim 1, wherein the second compound H comprises compound H1 having the polysulfide structure P.

5. The method for producing a laminate according to claim 4, wherein the compound H1 comprises a compound H11 represented by the following formula 6. HS-(R) １１ -Sx) ｎ -R １１ -SH...Form 6 (In the formula, R １１ ha-O-CH ２ A divalent organic group containing an -O- bond, or -CH ２ C(H)CH ２ - represents a trivalent organic group containing , where n is (R １１ The number of repetitions of -Sx) is an integer between 1 and 200, x is an integer between 1 and 5, and includes at least x=2, with the average value of x being greater than 1 and less than or equal to 2.

5.

6. The method for producing a laminate according to claim 1, wherein the primer layer forming composition further comprises a curing catalyst.

7. A method for producing a laminate according to any one of claims 1 to 6, wherein the content ratio of the epoxy group to the total number of moles of the epoxy group and the number of moles of the polysulfide structure P in the primer layer forming composition is 40 to 90 mol%.

8. In the primer layer formation step, the primer layer formation composition is applied to the asphalt waterproofing layer at a rate of 0.1 to 1.0 kg / m ２ A method for manufacturing a laminate according to claim 1, comprising applying the specified amount and curing it to form the primer layer.

9. A laminate provided on an asphalt waterproofing layer, the laminate comprising a primer layer on the asphalt waterproofing layer, a urethane coating waterproofing layer on the primer layer, and a topcoat layer on the urethane coating waterproofing layer, The primer layer comprises a reaction product of a first compound E having two or more epoxy groups in its molecule and a second compound H having two or more curable functional groups in its molecule that can react with epoxy groups, wherein the reaction product has a polysulfide structure P represented by the following formula 1. The aforementioned urethane coating waterproof layer is a laminate comprising a reaction product of an isocyanate-terminated prepolymer obtained by reacting a polyol with a polyisocyanate compound, and a compound having an active hydrogen-containing group. - (R) １０ -Sx)- ...Formula 1 (In the formula, R １０ (where represents a divalent or trivalent organic group, x represents an integer from 1 to 5, including at least x=2, and the average value of x is greater than 1 and less than or equal to 2.5.)

10. An asphalt waterproof layer with a urethane waterproofing material, comprising an asphalt waterproof layer and a urethane waterproofing material covering the asphalt waterproof layer, wherein the urethane waterproofing material includes the laminate described in claim 9.

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